High oil clear emulsion with diene elastomer

ABSTRACT

A clear antiperspirant and/or deodorant composition is disclosed in the form of an emulsion having a refractive index less than 1.42 and comprising: (a) 25-70% of an external phase comprising: (i) 0.1-10%, on an actives basis, of at least one elastomer which is a cyclomethicone (and) dimethicone crosspolymer made with an ≡Si—H containing polysiloxane and an alpha, omega-diene of formula CH 2 ═CH(CH 2 ) x CH═CH 2 , where x=1-20, to form a gel by crosslinking and addition of ≡Si—H across double bonds in the alpha, omega diene, which crosspolymer has a viscosity in the range of 50,000-3,000,000 centipoise; (ii) 0.1-5% of a silicone copolyol having an HLB value ≦8; (iii) 0.1-68% of a volatile silicone selected in an amount to complete the external phase; (iv) 0-10% of a cosurfactant or emulsifier having an HLB value in the range of 1-15; (v) 0-5% of a non-volatile silicone; and (b) 30-75% of an internal phase which is made with: (i) 7-25% (on an anhydrous actives basis (excluding the waters of hydration) of an antiperspirant active; (ii) 0-10% ethanol; (iii) additional water as required to adjust the refractive index; (iv) 0-5% of an antimicrobial agent; and (v) 0-5% of an ionizable salt; wherein the conductance of a water droplet applied to the surface of a thin film of the antiperspirant and/or deodorant composition is at least 250 micro Siemens/cm/ml as measured by a fixed geometry test at a loading of at least 7% by weight level of antiperspirant active.

FIELD OF THE INVENTION

This invention relates to clear antiperspirant and/or deodorant productswhich include an antiperspirant active ingredient and which providesbetter efficacy, stability and enhanced aesthetics. The compositions areemulsions made with an external (or oil) phase and an internal phasewhich contains the active ingredient. These emulsions may be used toform clear gel, soft solid or roll-on products.

BACKGROUND OF THE INVENTION

A large variety of antiperspirant and/or deodorant formulations havebeen described in the patent literature and/or have been madecommercially available. These products have included suspension as wellas emulsions. Also various physical forms may be used such as solids(for example, wax and sticks), semi-solids (for example, gels andcreams), liquids (for example, roll-on products) and sprays (bothaerosol and non-aerosol). In recent years a strong emphasis has beenplaced on improving both the performance and the aesthetics of theseproducts. One of the particular problems is trying to obtain an emulsionproduct that has efficacy comparable to suspension products. A secondproblem is the stabilization of emulsion products to achieve a productthat is shelf stable, but which releases an active ingredient in atimely manner.

With regard to emulsions, U.S. Pat. No. 4,673,570 to Soldati describesuniform, clear gelled antiperspirant compositions, free of waxes whereinthe emulsions comprise in combination a volatile silicone fluid, asilicone emulsifier (such as a mixture of cyclomethicone and dimethiconecopolyol), a destabilizing auxiliary emulsifier, water, a non-volatileemollient (such as C10-C20 alkyl fatty esters and ethers), linearsilicone fluids, a coupling agent (such as low molecular weight alcoholsand glycols), an active antiperspirant component and other ancillaryagents.

U.S. Pat. No. 5,008,103 to Raleigh et al describes water-in-oilantiperspirant emulsions having a discontinuous polar phase containingwater and optionally containing an emulsifier with ahydrophilic-lipophilic balance (HLB value) greater than 8, and avolatile silicone continuous phase with a dimethicone copolyolemulsifier. U.S. Pat. No. 5,401,870 to Raleigh et al and U.S. Pat. No.5,292,503 to Pereira et al describe similar subject matter.

U.S. Pat. No. 5,216,033 to Pereira et al describes a transparentwater-in-oil emulsion containing a silicone phase with a dimethiconecopolyol and an aqueous phase containing a refractive index“transparency structurant” to produce a refractive index matched clearemulsion. The transparency structurant is a C3-C8 polyhydric alcohol.

U.S. Pat. No. 5,989,531 describes a liquid composition made with (a) anactive phase comprising a selected glycol, a nonionic emulsifier havingan HLB value greater than 8 and an antiperspirant and/or deodorantactive; and (b) a silicone phase made with one or more of a dimethiconecopolyols having an HLB less than 7 and nonionic emulsifiers having anHLB greater than 7, wherein the silicone phase has at least 10% siliconeand the ratio of the silicone phase to the active phase is in the rangeof 1:1-1:4. Optional ingredients include the use of non-volatilesilicones, volatile silicones and organic emollients.

U.S. Pat. No. 6,010,688 discloses the use of polyhydric alcohols toimprove the stability and efficacy of antiperspirant formulations,particularly antiperspirant gels.

U.S. Pat. No. 5,955,065 discloses antiperspirant gel compositionscontaining soluble calcium salts. These compositions contain an aluminumor aluminum-zirconium antiperspirant salt and a water soluble calciumsalt, both of which are suspended in a dermatologically acceptableanhydrous carrier vehicle. The present invention also embraces a methodof inhibiting or reducing perspiration by topically applying aneffective amount of such an antiperspirant composition to the skin.

U.S. Pat. No. 5,925,338 discloses a clear antiperspirant or deodorantgel composition which exhibits reduced staining while retainingexcellent aesthetic attributes and efficacy. The oil phase comprisesabout 10 to 25% of the composition and contains a silicone oil and apolyether substituted silicone emulsifying agent. The silicone oilcomprises a mixture of a non-volatile silicone, preferably anon-volatile linear silicone, and a volatile linear silicone. It hasbeen found that reducing the amount of non-volatile silicone in theknown gel composition to a relatively low level (e.g. below about 5%)and adding an amount of volatile linear silicone to the composition(e.g. above about 2%, preferably above about 5%) substantially improvesthe non-staining properties of the composition.

U.S. Pat. No. 5,623,017 discloses a clear silicone gel cosmeticcomposition with a water-containing internal phase. The siliconeemulsifiers discussed are non-polymeric ethoxylated bis-trisiloxanes.

U.S. Pat. No. 6,007,799 discloses a clear cosmetic gel composition inthe form of a water-in-oil emulsion, comprising (a) a water-based phasecomprising water, a cosmetically active ingredient, and at least onecoupling agent; and (b) an oil-based phase comprising a material havinga refractive index in the range of 1.40-1.50, silicone fluids and analkoxylated, alkyl substituted siloxane surface active agent (e.g.,dimethicone copolyol). The composition has a refractive index in a rangeof 1.4026 to 1.4150. Where the cosmetically active ingredient is anantiperspirant active ingredient, the composition can be anantiperspirant gel (for example, soft gel) composition. In therefractive index range of the present invention, increased amounts of,for example, antiperspirant active ingredient, and otherhigh-refractive-index materials providing cosmetic benefits, can beincorporated in the water and oil phases of the composition while stillachieving a clear composition. The composition can also includepolypropylene glycols (for example, tripropylene glycol), as part of thewater-based phase, to provide a composition having reduced tackiness andreduced whitening (decreased residue); this composition is also mild.

U.S. Pat. No. 5,587,173 discloses a clear gel-type cosmetic productwhich has a viscosity of at least about 50,000 centipoise (cps) at 21°C., and includes an emulsion with an oil phase and a water phase thatincludes an incorporated active ingredient. The refractive indices ofthe water and oil phases match to at least 0.0004, the refractive indexof the product is about 1.4000, and the product clarity is better thanthirty NTU. These formulas contain 75-90% dispersed active phase. Seealso U.S. Pat. No. 4,021,536: which describes magnesium-zirconiumcomplexes useful as antiperspirants; and U.S. Pat. No. 5,463,098 whichdescribes clear antiperspirant gel stick and method for making same.

U.S. Pat. No. 3,979,510 describes aluminum-zirconium antiperspirantsystems with complex aluminum buffers, including the use of variousdivalent metal ions in aluminum-zirconium antiperspirant formulations.

U.S. Pat. No. 4,980,156 discloses improved dry-feeling antiperspirantcompositions which comprise an aqueous solution of an astringentemulsified in a volatile silicon fluid. The emulsion is stabilized byusing a combination of a long-chain alkyl modifiedpolysiloxane-polyoxyalkylene copolymer and an organic surfactant havingan HLB value from 8 to 18.

U.S. Pat. No. 4,673,570 discloses uniform, clear gelled antiperspirantcompositions, free of waxes and conventional gelling agents. The gelemulsions comprise, in combination, a volatile silicone fluid, asilicone emulsifier, a destabilizing auxiliary emulsifier, water, anon-volatile emollient, a coupling agent, an active antiperspirantcomponent and ancillary agents.

U.S. Pat. No. 5,454,026 discloses a clear antiperspirant gel which ismade by combining (a) an astringent compound having a refractive indexof 1.48 to 1.53 which is an antiperspirant salt in the form of (i) atray dried compound, (ii) an encapsulated salt, or (iii) a solventsolution of a salt compound; and (b) a clear anhydrous organic oil-freegel formed with 12-hydroxystearic acid as the gelling agent and a blendof aromatic containing silicone fluid and volatile silicone fluids.

U.S. Pat. No. 5,587,153 broadly discloses clear antiperspirant gels witha refractive index of 1.3975 to 1.4025 and a viscosity of 50,000-200,000centipoise which are emulsions having 75-90% of a water phase.

U.S. Pat. No. 5,563,525 also discloses clear antiperspirant gels havinga viscosity of at least 50,000 centipoise and a clarity better than 50NTU which are emulsions having 75-90% of a water phase.

U.S. Pat. No. 6,060,546 to Powell et al describes a non-aqueous siliconeemulsion containing a silicone phase and an organic phase in which thesilicone phase contains a crosslinked silicone elastomer and the organicphase may contain up to 50% water.

U.S. Pat. No. 6,103,250 describes an anhydrous composition comprising1-50% of a polar, emulsifying siloxane elastomer, 0.01-40% particulatematerial, and 1-70% of a nonpolar oil, wherein the elastomer is presentin an amount to render the incompatible nonaqueous polar ingredientcompatible in the anhydrous composition.

U.S. Pat. No. 5,922,308 to Brewster et al describes an underarmcomposition comprising 0.1-5.5% of a crosslinked non-emulsifyingsiloxane elastomer and 10-80% of volatile siloxane.

Historically, suspension products such as sticks have exhibited betterefficacy than emulsion products. Previous attempts have not successfullyovercome the problems of improving efficacy and achieving satisfactoryformation of emulsions.

As an additional aspect of the invention, it has heretofore beendifficult to obtain a clear emulsion when an elastomer was present.Also, it was been very difficult to get the elastomer to mixsatisfactorily in an emulsion environment and the elastomer particlestend to still remain as isolated particles.

Examples of elastomer compositions include the following. PCT case WO97/44010 and assigned to the same assignee as this application describesa silicone gel material made by combining (a) a volatile siliconematerial and (b) an organopolysiloxane material (or silicone elastomer)as a gelling agent wherein the organopolysiloxane material (siliconeelastomer) can be a reaction product of a vinyl-terminated siloxanepolymer and a silicon hydride cross-linking agent. Related technology isalso disclosed in PCT case WO 98/00097, WO 98/00104 and 98/00105assigned to Unilever PLC on cross-linked non-emulsifying elastomers.

U.S. Pat. No. 5,599,533 to Stepniewski et al assigned to Estee Lauderdescribes a stable water-in-oil emulsion system formed with anorganopolysiloxane elastomer, a vehicle in which the elastomer isdispersed or dispersible, a stabilizing agent, a surfactant and anaqueous component. A commercial product known as “REVELATION”retexturizing complex for hands and chest sold by the same assigneecontains a silicone gel material with an organopolysiloxane componentand octamethylcyclotetrasiloxane. This reference does not teach a clearcomposition and also teaches that you have to cap the electrolyte at 5%.In addition, this reference relies on polyols and alcohols asstabilizing agents.

EP 0 787 758 A1 teaches a method for solvent thickening by using asilicone latex having a plurality of crosslinked polysiloxane particles.

Another recent case assigned to the same assignee as this application isWO 99/51192 and U.S. patent application Ser. No. 9/273152 whichdescribes antiperspirant compositions with the use of broad categoriesof elastomers. Other examples of the use of elastomer type materialsand/or methods for processing such materials may be found in PCT casesWO 98/00097; WO 98/00104; WO 98/00105; WO 98/18438; WO 98/42307 all ofwhich are incorporated herein by reference.

Thus, it is an object of this invention to provide improved emulsionscontaining 25%-70% of an oil phase which exhibit improved efficacy whichefficacy is comparable to that achieved in suspension products and, atthe same time, have a stability profile that allows for satisfactorystability on the shelf. Another issue is the formation of emulsionswhich are stable on the shelf but which destabilize sufficiently afterapplication to a skin surface so as to release an efficacious amount ofan active ingredient. Thus, it is an object of the present invention toprovide emulsions with those characteristics as well as enhancedaesthetics such as smoothness in application, low tack and dry feel. Itis also an object of this invention to provide gel or soft solidcompositions which can, if desired, be formed into clear compositionseven with the presence of selected elastomer materials. It is stillanother object of this invention to provide compositions that can, ifdesired, be formed into clear compositions without the use ofmicroemulsions.

SUMMARY OF THE INVENTION

This invention relates to a clear antiperspirant and/or deodorantcomposition in the form of a water-in-oil emulsion having a refractiveindex less than 1.42 and comprising:

(a) 25-70% (particularly with a high oil content of 25-50%, and moreparticularly 30-45%) of an external phase (also called the oil phase orthe continuous phase) which is made with:

(i) 0.1-10% (on an actives basis) of at least one elastomer which is acyclomethicone (and) dimethicone crosspolymer made with an ≡Si—Hcontaining polysiloxane and an alpha, omega-diene of formulaCH₂═CH(CH₂)_(x)CH═CH₂, where x=1-20, to form a gel by crosslinking andaddition of ≡Si—H across double bonds in the alpha, omega diene, whichcrosspolymer has a viscosity in the range of 50,000-3,000,000 centipoise(particularly 100,000-1,000,000; more particularly 250,000-450,000centipoise; and most particularly 350,000 centipoise), preferably with anonvolatiles content of 8-18% (particularly 10-14% and most particularly12-13%) in cyclomethicone (for example a D4 or D5 cyclomethicone), (anexample of such a crosspolymer composition being DC-9040 from DowCorning Corporation (Midland, Mich.) with other types of suchcrosspolymers (also called elastomers) being described in U.S. Pat. No.5,654,362, incorporated by reference herein as to the description ofsuch polymers and methods of making such polymers);

(ii) 0.1-5% (particularly 0.1-1.0%) of a silicone copolyol having an HLBvalue (hydrophilic lipophilic balance)≦8;

(iii) 0.1-68% of a volatile silicone selected in an amount to completethe external phase;

(iv) 0-10% (particularly 0-5%) of a cosurfactant or emulsifier having anHLB value in the range of 1-15;

(v) 0-5% of a non-volatile silicone; and

(b) 30-75% (particularly 50-75%) of an internal phase (also calledactives phase or dispersed phase) which is made with:

(i) 7-25% (on an anhydrous actives basis excluding the waters ofhydration) of an antiperspirant active preferably added as a solution ofactive in water and/or water+glycol mixture as a solvent;

(ii) 0-10% ethanol;

(iii) additional water as needed to adjust the refractive index;

(iv) 0-5% of an antimicrobial agent; and

(v) 0-5% of an ionizable salt;

wherein (1) the conductance of a water droplet applied to the surface ofa thin film of the antiperspirant and/or deodorant composition is atleast 250 micro Siemens/cm/ml as measured by the fixed geometry testdescribed below at a loading of at least 7% by weight level ofantiperspirant active (with more particular embodiments havingconductances greater than 300 micro Siemens/cm/ml, particularly greaterthan 400 micro Siemens/cm/ml and especially greater than 500 microSiemens/cm/ml.); and (2) all amounts are in percent by weight based onthe total weight of the composition unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

The clear cosmetic compositions of this invention having a refractiveindex less than 1.42 are made with 25-70 (particularly 25-50% and, moreparticularly, 30-45%) of an external phase and 30-75% (particularly50-75% and, more particularly, 55-70%) of an internal phase.Alternatively, another specific embodiment can include 40-70% and moreparticularly 50-60% of an external phase; and 30-60% and moreparticularly 40-50% of an internal phase.

The elastomer component described above is used in an amount of 0.1-10%(on an actives basis) particularly in an amount of 1-7% and, moreparticularly, in an amount of 1-5%. One particular elastomer of interestis DC 9040 from Dow Corning Corporation (Midland, Mich.). Frequently theelastomer is obtained as a mixture in cyclomethicone.

A silicone copolyol (especially dimethicone copolyol) may be used in anamount of 0.1-5% (actives basis), particularly 0.1-3% and, moreparticularly, 0.1-1.0%.

In general, silicone copolyols useful in the present invention includecopolyols of the following Formulae I and II. Formula I materials may berepresented by:

(R¹⁰)₃—SiO—[(R¹¹)₂—SiO]_(x)—[Si(R¹²)(R^(b)—O—(C₂H₄O)_(p)—(C₃H₆O)_(s)—R^(c))O]_(y)—Si—(R¹³)₃  FormulaI

wherein each of R¹⁰, R¹¹, R¹² and R¹³ may be the same or different andeach is selected from the group consisting of C1-C6 alkyl; R^(b) is theradical —C_(m)H_(2m)—; R^(c) is a terminating radical which can behydrogen, an alkyl group of one to six carbon atoms, an ester group suchas acyl, or an aryl group such as phenyl; m has a value of two to eight;p and s have values such that the oxyalkylene segment—(C₂H₄O)_(p)—(C₃H₆O)_(s)— has a molecular weight in the range of 200 to5,000; the segment preferably having fifty to one hundred mole percentof oxyethylene units —(C₂H₄O)_(p)— and one to fifty mole percent ofoxypropylene units —(C₃H₆O)_(s)—; x has a value of 8 to 400; and y has avalue of 2 to 40. Preferably each of R¹⁰, R¹¹, R¹² and R¹³ is a methylgroup; R^(c) is H; m is preferably three or four whereby the group R^(b)is most preferably the radical —(CH₂)₃—; and the values of p and s aresuch as to provide a molecular weight of the oxyalkylene segment—(C₂H₄O)_(p)—(C₃H₆O)_(s)— of between about 1,000 to 3,000. Mostpreferably p and s should each have a value of about 18 to 28.

A second siloxane polyether (copolyol) has the Formula II:

(R¹⁰)₃—SiO—[(R¹¹)₂—SiO]_(x)—[(Si(R¹²)(R^(b)—O—(CH₂H₄O)_(p)R^(c))O]_(y)]—Si—(R¹³)₃  FormulaII

wherein p has a value of 6 to 16; x has a value of 6 to 100; and y has avalue of 1 to 20 and the other moieties have the same definition asdefined in Formula I.

It should be understood that in both Formulas I and II shown above, thatthe siloxane-oxyalkylene copolymers of the present invention may, inalternate embodiments, take the form of endblocked polyethers in whichthe linking group R^(b), the oxyalkylene segments, and the terminatingradical R^(c) occupy positions bonded to the ends of the siloxane chain,rather than being bonded to a silicon atom in the siloxane chain. Thus,one or more of the R¹⁰, R¹¹, R¹² and R³ substituents which are attachedto the two terminal silicon atoms at the end of the siloxane chain canbe substituted with the segment —R^(b)—O—(C₂H₄O)_(p)—(C₃H₆O)_(s)—R^(c)or with the segment —R^(b)—O—(C₂H₄O)_(p)—R^(c). In some instances, itmay be desirable to provide the segment—R^(b)—O—(C₂H₄O)_(p)—(C₃H₆O)_(s)—R^(c) or the segment—R^(b)—O—(C₂H₄O)_(p)—R^(c) at locations which are in the siloxane chainas well as at locations at one or both of the siloxane chain ends.

Particular examples of suitable dimethicone copolyols are availableeither commercially or experimentally from a variety of suppliersincluding Dow Corning Corporation, Midland, Mich.; General ElectricCompany, Waterford, N.Y.; Witco Corp., Greenwich, Conn.; and GoldschmidtChemical Corporation, Hopewell, Va. Examples of specific productsinclude DOW CORNING® 5225C from Dow Corning which is a 10% dimethiconecopolyol in cyclomethicone; DOW CORNING® 2-5185C which is a 45-49%dimethicone copolyol in cyclomethicone; SIL WET L-7622 from Witco; ABILEM97 from Goldschmidt which is a 85% dimethicone copolyol in D5cyclomethicone; and various dimethicone copolyols available eithercommercially or in the literature.

It should also be noted that various concentrations of the dimethiconecopolyols in cyclomethicone can be used. While a concentration of 10% incyclomethicone is frequently seen commercially, other concentrations canbe made by stripping off the cyclomethicone or adding additionalcyclomethicone. The higher concentration materials such as DOW CORNING®2-5185 material is of particular interest.

In one particular embodiment 0.1-5% (particularly 1.0-5.0%) of a 10-50%silicone copolyol such as dimethicone copolyol in cyclomethicone mixturemay be used, wherein the amount of mixture added is selected so that thelevel of silicone copolyol in the cosmetic composition is in the rangeof 0.25-5.0% (particularly 1%) (for example, 0.25-10% of a 40%-50%dimethicone copolyol in cyclomethicone mixture).

For the volatile silicone component, an amount of 0.1-68% may be usedplus an incremental amount to complete the selected amount of theexternal phase (quantum sufficient or “q.s.”). Particular ranges include10-58%, (more particularly 10-50% and, even more particularly, 15-30%)by weight based on the entire weight of the composition which may beused. By volatile silicone material is meant a material that has ameasurable vapor pressure at ambient temperature. For the volatilesilicone portion, examples of volatile silicones (particularly siliconeswith a boiling point of 250 degrees C. or less at atmospheric pressure)include cyclomethicone (especially cyclopentasiloxane, also called“D5”), “hexamethyldisiloxane”, and low viscosity dimethicone (forexample, Dow Corning® 200 fluid having a viscosity of 1-200centistokes). Such volatile silicones include conventional cyclic andlinear volatile silicones Illustratively, and not by way of limitation,the volatile silicones are one or more members selected from the groupconsisting of cyclic polydimethylsiloxanes such as those represented byFormula III:

where n is an integer with a value of 3-7, particularly 5-6. Forexample, DC-245 fluid (or the DC-345 version) from Dow CorningCorporation (Midland, Mich.) is a type of cyclomethicone which can beused. These include a tetramer (or octylmethylcyclotetrasiloxane) and apentamer (or decamethylcyclopentasiloxane). The volatile linearsilicones can also be included in this group of volatile silicones andare one or more members selected from the group consisting of linearpolydimethylsiloxanes such as those represented by Formula IV:

and t is selected to obtain a viscosity of 1-200 centistokes.

The co-surfactants used in this invention (which can also be a mixtureor blend of surfactants) include, but are not limited to at least onemember selected from the group consisting of:

(a) sorbitan esters and ethoxylated sorbitan esters (for example PEG-20sorbitan isostearate, sorbitan monolaurate, polysorbate-20,polysorbate-40, polysorbate-60, polysorbate-80);

(b) ethoxylates (for example, Ceteth-20, PEG-30 castor oil, PEG-40hydrogenated castor oil, PEG-60 hydrogenated castor oil, Laureth-7,Isolaureth-6, Steareth-10, Steareth-20, Steareth-21, Steareth-100,Ceteareth-12, Oleth-5, Oleth-10, and Oleath-20);

(c) ethoxylated adducts (for example, PEG-25 stearate, glyceryl stearateand PEG-100 stearate);

(d) PEG esters (for example, PEG-8 oleate, PEG-8 laurate, PEG-8dilaurate, PEG-12 dilaurate, PEG-80 diisostearate, PEG-40 stearate);

(e) propoxylates (for example, PPG-10 butanediol, PPG-50 oleyl ether,PPG-2-ceteareth-9, PPG-3-deceth-3, PPG-5-ceteth-20);

(f) ethoxylated modified triglycerides (for example, PEG-20 cornglycerides, PEG-12 palm kernel glycerides);

(g) alkylphenol aromatic ethoxylates (for example, dinonylphenolethoxylate with 9 moles of EO, octylphenol ethoxylate with 20 moles ofEO, octylphenol ethoxylate with 40 moles of EO); and

(h) block copolymers which are alkoxylated glycols having ethoxylatedand propoxylated segments (for example, Poloxamers 182 and 234, andMeroxapol 174); wherein the nonionic surfactant is selected so that ithas an HLB (hydrophilic-lipophilic balance) value in the range of 1-15.

The HLB parameter is a well known parameter the calculation of which isdisclosed and explained in numerous references. For nonionicsurfactants, data obtained by actual analysis is usually a more accuratemeasure of HLB values (rather than theoretical determinations). Forpurposes of this invention it is intended that either the actual ortheoretical HLB value may be used as the basis for selection.

For the co-surfactant having an HLB value ≦8, examples include:

(a) ethoxylated alcohols such as steareth-2, Oleth-3, nonoxynol-2,PPG-4-Ceteth-1;

(b) ethoxylated carboxylic acids such as PEG-4 dilaurate, PEG-2 oleate;

(c) glyceryl esters such as PEG-2 castor oil, PEG-7 hydrogenated castoroil, glyceryl monooleate, glyceryl monostearate, triglycerol monooleate,decaglyceryl tetraoleate, and polyglyceryl-3 oleate, glyceryl stearate;

(d) sorbitan derivatives such as sorbitan oleate, sorbitan monostearate,sorbitan tristearate, sorbitan monooleate, sorbitol trioleate, sorbitanmonotallate, sorbitan isostearate;

(e) sugar esters such as sucrose distearate; and

(f) lanolin alcohol.

The surfactant or blend of surfactants incorporated into thecompositions of the present invention can, illustratively, be includedin amounts of 0.1-20%, preferably 0.5-10%, and more preferably 1-5%, byweight based on the total weight of the composition.

The non-volatile silicone component may be used as an optional emollientor to match the refractive index. Examples of non-volatile silicones(that is, silicones with a boiling point above 250 degrees C. atatmospheric pressure) include phenyl trimethicone, dimethicone,phenylpropyltrimethicone (SF1555 from General Electric, Waterford,N.Y.), cetyl dimethicone, and dimethiconol as well as two or more of theforgoing.

For the antiperspirant active used in the internal (also called“active”) phase various antiperspirant active materials that can beutilized according to the present invention provided that they aresoluble at a suitable concentration in the active phase. These includeconventional aluminum and aluminum/zirconium salts, as well asaluminum/zirconium salts complexed with a neutral amino acid such asglycine, as known in the art. See each of European Patent ApplicationNumber. 512,770 A1 and PCT case WO 92/19221, the contents of each ofwhich are incorporated herein by reference in their entirety, fordisclosure of antiperspirant active materials. The antiperspirant activematerials disclosed therein, including the acidic antiperspirantmaterials, can be incorporated in the compositions of the presentinvention if they are soluble in the active phase. Suitable materialsinclude (but are not limited to) aluminum chlorides (various typesincluding, for example, anhydrous form, hydrated form, etc.), zirconylhydroxychlorides, zirconyl oxychlorides, basic aluminum chlorides, basicaluminum chlorides combined with zirconyl oxychlorides andhydroxychlorides, and organic complexes of each of basic aluminumchlorides with or without zirconyl oxychlorides and hydroxychlorides andmixtures of any of the foregoing. These include, by way of example (andnot of a limiting nature), aluminum chlorohydrate, aluminum chloride,aluminum sesquichlorohydrate, aluminum chlorohydrol-propylene glycolcomplex, zirconyl hydroxychloride, aluminum-zirconium glycine complex(for example, aluminum zirconium trichlorohydrex gly, aluminum zirconiumpentachlorohydrex gly, aluminum zirconium tetrachlorohydrex gly andaluminum zirconium octochlorohydrex gly), aluminum dichlorohydrate,aluminum chlorohydrex PG, aluminum chlorohydrex PEG, aluminumdichlorohydrex PG, aluminum dichlorohydrex PEG, aluminum zirconiumtrichlorohydrex gly propylene glycol complex, aluminum zirconiumtrichlorohydrex gly dipropylene glycol complex, aluminum zirconiumtetrachlorohydrex gly propylene glycol complex, aluminum zirconiumtetrachlorohydrex gly dipropylene glycol complex, and mixtures of any ofthe foregoing. The aluminum-containing materials can be commonlyreferred to as antiperspirant active aluminum salts. Generally, theforegoing metal antiperspirant active materials are antiperspirantactive metal salts. In the embodiments which are antiperspirantcompositions according to the present invention, such compositions neednot include aluminum-containing metal salts, and can include otherantiperspirant active materials, including other antiperspirant activemetal salts. Generally, Category I active antiperspirant ingredientslisted in the Food and Drug Administration's Monograph on antiperspirantdrugs for over-the-counter human use can be used. In addition, any newdrug, not listed in the Monograph, such as tin or titanium salts usedalone or in combination with aluminum compounds (for example,aluminum-stannous chlorohydrates), aluminum nitratohydrate and itscombination with zirconyl hydroxychlorides and nitrates, can beincorporated as an antiperspirant active ingredient in antiperspirantcompositions according to the present invention. Preferredantiperspirant actives that can be incorporated in the compositions ofthe present invention include the enhanced efficacy aluminum salts andthe enhanced efficacy aluminum/zirconium salt-glycine materials, havingenhanced efficacy due to improved molecular distribution, known in theart and discussed, for example, in PCT No. WO92/19221, the contents ofwhich are incorporated by reference in their entirety herein. Particularactives include Westchlor A2Z 4105 aluminum zirconium tetrachlorohydrexgly propylene glycol complex, (from Westwood Chemical Corporation,Middletown, N.Y.); Westchlor ZR 35B aluminum zirconium tetrachlorhydrexgly, and Rezal 36 GP and AZP 902 aluminum zirconium tetrachlorhydrex glyboth from Reheis, Berkeley Heights, N.J. as well as Rezal AZZ 908 fromReheis. In general, the metal:chloride mole ratio is in the range of2.1-0.9:1 for such salts.

Actives of special interest because they form low RI solutions include:Westchlor Zr 35BX3 (30-35% actives in water) from Westwood ChemicalCompany, Middletown, N.Y.; Rezal 36G (46% in water) from Reheis Inc.,Berkeley Heights, N.J.; Summit AZG-368 (28-32% in water) from SummitResearch Labs, Huguenot, N.Y.; Reach 301 (39% in water) from ReheisInc.; and aluminum chloride (28% in water) which may be obtained fromseveral sources. In general, the metal:chloride mole ratio isapproximately 1.4:1 for such salts.

In one particular type of salt of interest, an aluminum zirconium tetrasalt with glycine is used wherein aluminum zirconium tetrachlorohydrexglycine salt having a metal to chloride ratio in the range of 0.9-1.2:1(especially in the range of 0.9-1.1:1 and, more particularly in therange of 0.9-1.0:1); and a glycine:zirconium mole ratio greater than1.3:1, particularly greater than 1.4:1. This type of salt may be made ina variety of ways as described in co-pending case IR 6558 filed on thesame day as this application.:

Method A: An aluminum chlorohydrate (ACH) solution of ACH salt in waterof suitable concentration is mixed with an aqueous solution of zirconylchloride (ZrOCl₂) of suitable concentration and powdered glycine. Themixture is stirred at room temperature to obtain the salt.

Method B: A suitable commercially available aluminum zirconiumtetrachlorohydrex glycine salt is obtained and mixed with a sufficientamount of an aqueous aluminum chloride (AlCl₃) solution and powderedglycine. The mixture is stirred at room temperature to obtain the salt.When Method B is used, a suitable salt to use as a starting materialincludes various types of tetra salts such as aluminum zirconiumtetrachlorohydrex gly, aluminum zirconium tetrachlorohydrex glypropylene glycol complex, aluminum zirconium tetrachlorohydrex glydipropylene glycol complex, and mixtures of any of the foregoing . Thesesalts will be referred to hereinafter as experimental salts or carry an“exp” suffix in their designation. It is preferred that the experimentalsalt be used in the form of a 28-50% water solution when added to formthe compositions of the invention.

Method C: An aqueous aluminum chlorohydrate (ACH) solution made from anactivated ACH salt of suitable concentration is mixed with an aqueoussolution of zirconyl chloride (ZrOCl₂) of suitable concentration andpowdered glycine. The mixture is stirred at room temperature for a shortperiod of time and then spray dried to obtain the salt in powder form.

Mixtures of actives can also be used, provided a suitable amount of lowRI material is used to achieve a satisfactory product.

Antiperspirant actives can be incorporated into compositions accordingto the present invention in amounts in the range of 7-25% (on ananhydrous solids basis), preferably 7-20%, by weight, of the totalweight of the composition. The amount used will depend on theformulation of the composition. At amounts at the higher end of therange (especially in a range of 9-20% or 9-25%, a good antiperspiranteffect can be expected. As noted above, the active is preferablyincluded in the compositions of the invention by premixing the activewith water and possibly small amount of propylene glycol.

Deodorant active materials can also be included such as:

(a) fragrances, such as in the range of 0.5-3.0 percent by weight basedon the total weight of the composition;

(b) effective amounts of antimicrobial agents, for example, 0.05-5.0percent (particularly 0.1-1% and, more particularly, 0.25-1.0%) byweight based on the total weight of the composition; examples includebacteriostatic quaternary ammonium compounds (such as cetyltrimethyl-ammonium bromide, and cetyl pyridinium chloride),2,4,4′-trichloro-2′-hydroxydiphenylether (Triclosan),N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl) urea (Triclocarban), silverhalides, octoxyglycerin (SENSIVA™ SC 50) and various zinc salts (forexample, zinc ricinoleate). Triclosan or Triclocarban can,illustratively, be included in an amount of from 0.05% to about 0.5% byweight, of the total weight of the composition; or

(c) effective amounts of a masking agent, such as 0.1-5%.

While it has been described that the water component of the inventionmay also contain a minor amount of a glycol component such as propyleneglycol, it is preferred that no added glycol be used. The glycolcomponent, if included, is comprised of one or more glycols and/or apolyglycols selected from the group consisting of ethylene glycol,propylene glycol, 1,2-propanediol, diethylene glycol, triethyleneglycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol,methyl propanediol, 1,6-hexanediol, 1,3-butanediol, 1,4-butanediol,PEG-4 through PEG-100, PPG-9 through PPG-34, pentylene glycol, neopentylglycol, trimethylpropanediol, 1,4-cyclohexanedimethanol,2,2-dimethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol,and mixtures thereof. More particular examples of the glycol componentinclude one or more members of the group consisting of propylene glycol,dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol,methyl propylene glycol, low molecular weight (less than 600)polyethylene glycol, low molecular weight (less than 600) polypropyleneglycols, and mixtures of any of the foregoing. Propylene glycol is ofparticular interest because the antiperspirant active is more soluble inthis type of glycol. Tripropylene glycol has lower irritancy, but theantiperspirant active is not as soluble in this glycol. Methyl propyleneglycol is also of interest. Mixtures of glycols may be used to balancethese desirable properties.

The compositions of the present invention can also include otheroptional ingredients to improve the aesthetics and/or performance of thecosmetic compositions of the invention. These include emollients,thickeners, colorants, fillers, fragrances, masking agents, etc.

Emollients are a known class of materials in this art, imparting asoothing effect to the skin. These are ingredients which help tomaintain the soft, smooth, and pliable appearance of the skin.Emollients are also known to reduce whitening on the skin and/or improveaesthetics. Examples of chemical classes from which suitable emollientscan be found include:

(a) fats and oils which are the glyceryl esters of fatty acids, ortriglycerides, normally found in animal and plant tissues, includingthose which have been hydrogenated to reduce or eliminate unsaturation.Also included are synthetically prepared esters of glycerin and fattyacids. Isolated and purified fatty acids can be esterified with glycerinto yield mono-, di-, and triglycerides. These are relatively pure fatswhich differ only slightly from the fats and oils found in nature. Thegeneral structure may be represented by Formula VI:

wherein each of R¹, R², and R³ may be the same or different and have acarbon chain length (saturated or unsaturated) of 7 to 30. Specificexamples include peanut oil, sesame oil, avocado oil, coconut, cocoabutter, almond oil, safflower oil, corn oil, cotton seed oil, castoroil, hydrogenated castor oil, olive oil, jojoba oil, cod liver oil, palmoil, soybean oil, wheat germ oil, linseed oil, and sunflower seed oil;

(b) hydrocarbons which are a group of compounds containing only carbonand hydrogen. These are derived from petrochemicals. Their structurescan vary widely and include aliphatic, alicyclic and aromatic compounds.Specific examples include paraffin, petrolatum, hydrogenatedpolyisobutene, and mineral oil.

(c) esters which chemically, are the covalent compounds formed betweenacids and alcohols. Esters can be formed from almost all acids(carboxylic and inorganic) and any alcohol. Esters here are derived fromcarboxylic acids and an alcohol. The general structure would beR⁴CO—OR⁵. The chain length for R⁴ and R⁵ can vary from 7 to 30 and canbe saturated or unsaturated, straight chained or branched. Specificexamples include isopropyl myristate, isopropyl palmitate, isopropylstearate, isopropyl isostearate, butyl stearate, octyl stearate, hexyllaurate, cetyl stearate, diisopropyl adipate, isodecyl oleate,diisopropyl sebacate, isostearyl lactate, C₁₂₋₁₅ alkyl benzoates,myreth-3 myristate, dioctyl malate, neopentyl glycol diheptanoate,dipropylene glycol dibenzoate, C₁₂₋₁₅ alcohols lactate, isohexyldecanoate, isohexyl caprate, diethylene glycol dioctanoate, octylisononanoate, isodecyl octanoate, diethylene glycol diisononanoate,isononyl isononanoate, isostearyl isostearate, behenyl behenate, C₁₂₋₁₅alkyl fumarate, laureth-2 benzoate, propylene glycol isoceteth-3acetate, propylene glycol ceteth-3 acetate, octyldodecyl myristate,cetyl ricinoleate, myristyl myristate.

(d) saturated and unsaturated fatty acids which are the carboxylic acidsobtained by hydrolysis of animal or vegetable fats and oils. These havegeneral structure R⁶COOH with the R⁶ group having a carbon chain lengthbetween 7 and 30, straight chain or branched. Specific examples includelauric, myristic, palmitic, stearic, oleic, linoleic and behenic acid.

(e) saturated and unsaturated fatty alcohols (including guerbetalcohols) with general structure R⁷COH where R⁷ can be straight orbranched and have carbon length of 7 to 30. Specific examples includelauryl, myristyl, cetyl, isocetyl, stearyl, isostearyl, oleyl,ricinoleyl and erucyl alcohol;

(f) lanolin and its derivatives which are a complex esterified mixtureof high molecular weight esters of (hydroxylated) fatty acids withaliphatic and alicyclic alcohols and sterols. General structures wouldinclude R⁸CH₂—(OCH₂CH₂)_(n)OH where R⁸ represents the fatty groupsderived from lanolin and n=5 to 75 or R⁹CO—(OCH₂CH₂)_(n) OH where R⁹CO-represents the fatty acids derived from lanolin and n=5 to 100. Specificexamples include lanolin, lanolin oil, lanolin wax, lanolin alcohols,lanolin fatty acids, isopropyl lanolate, ethoxylated lanolin andacetylated lanolin alcohols.

(g) alkoxylated alcohols wherein the alcohol portion is selected fromaliphatic alcohols having 2-18 and more particularly 4-18 carbons, andthe alkylene portion is selected from the group consisting of ethyleneoxide, and propylene oxide having a number of alkylene oxide units from2-53 and, more particularly, from 2-15. Examples include cetyl glycerylether; isostearyl glyceryl ether; isostearyl glyceryl pentaerythritylether; laureth-5 butyl ether; oleyl glyceryl ether; PEG-4 ditallowether; polyglyceryl-3 cetyl ether; polyglyceryl-4 lauryl ether; PPG-9diglyceryl ether; propylene glycol myristyl ether. More specificexamples include PPG-14 butyl ether, PPG-53 butyl ether laureth-5 butylether and PEG-4 ditallow ether.

(h) ethers selected from the group consisting of dicaprylyl ether;dicetyl ether; dimethyl ether; distearyl ether; ethyl ether; isopropylhydroxycetyl ether; methyl hexyl ether; polyvinyl methyl ether;

(i) silicones and silanes the linear organo-substituted polysiloxaneswhich are polymers of silicon/oxygen with general structure:

(1) (R¹⁰)₃SiO(Si(R¹¹)₂O)_(x)Si(R¹²)₃ where R¹⁰, R¹¹ and R¹² can be sameor different and are each independently selected from the groupconsisting of phenyl and C1-C60 alkyl;

(2) HO(R¹⁴)₂SiO(Si(R¹⁵)₂O)_(x)Si(R¹⁶)₂OH, where R¹⁴, R¹⁵ and R¹⁶ can bethe same or different and are each independently selected from the groupconsisting of phenyl and C1-C60 alkyl; or

(3) organo substituted silicon compounds of formula R¹⁷Si(R¹⁸)OSiR¹⁹which are not polymeric where R¹⁷, R¹⁸ and R¹⁹ can be the same ordifferent and are each independently selected from the group consistingof phenyl and C1-C60 alkyl optionally with one or both of the terminal Rgroups also containing an hydroxyl group. Specific examples includedimethicone, dimethiconol behenate, C₃₀₋₄₅ alkyl methicone,stearoxytrimethylsilane, phenyl trimethicone and stearyl dimethicone.

(j) adipic acid blends selected from the group consisting of trimethylpentanediol/adipic acid copolymer (LEXOREZ TL8 from Inolex,Philadelphia, Pa.); trimethyl pentanediol/adipic acid/isononanoic acidcopolymer (LEXOREZ TC8); and adipic acid/diethylene glycol/glycerincrosspolymer (LEXOREZ 100);

(k) mixtures and blends of two or more of the foregoing.

Particular examples of suitable emollients include members of the groupconsisting of Octyloxyglyderin (SENSIVA SC50 from Schülke Mayr,Norderstedt, Germany) (which can be used as an emollient as well as anantibacterial); Polysorbate 80 (TWEEN 80 from ICI Americas, Wilmington,Del.); Oleth-20; ethoxylated alcohols such as steareth-2, nonoxynol-2,PPG-4-Ceteth-1; ethoxylated carboxylic acids such as PEG-4 dilaurate,PEG-2 oleate; glyceryl esters such as PEG-2 castor oil, polyglyceryl-3oleate, glyceryl stearate; sorbitan derivatives such as sorbitan oleate;PPG-3 myristyl ether (such as WITCONOL APM from Goldschmidt), adimethiconol (such as Dow Coming® DC1501 dimethiconol), neopentyl glycoldiheptanoate, PEG-8 laurate, isocetyl stearate, dimethicone copolyollaurate, Dow Corning 2501 cosmetic wax (dimethicone copolyol);isostearyl isostearate, isostearyl palmitate, isostearyl alcohol,PPG-5-ceteth-20, PPG-10-cetyl ether, triethyl hexanoin, ethyl hexylisostearate, glyceryl oleate, and isopropyl isostearate.

The emollient or emollient mixture or blend thereof incorporated incompositions according to the present invention can, illustratively, beincluded in amounts of 0.5-50%, preferably 1-25%, more preferably 3-5%,by weight, of the total weight of the composition.

As described above, water is used to make the solution of antiperspirantactive and an additional amount of water may be added as needed toadjust the refractive index. The total amount of water from all sourcesmay be present, for example in the range of 15-55%, particularly 40-55%.In a further optional aspect of the invention, the water also maycomprise up to 5% (based on the entire composition) of an ionizable saltof the form M_(a)X_(b) where a=1 or 2; b=1 or 2; M is a member selectedfrom the group consisting of Na⁺¹, Li⁺¹, K⁺¹, Mg⁺², Ca⁺², Sr⁺², Sn⁺²,and Zn⁺²; and X is a member selected from the group consisting ofchloride, bromide, iodide, citrate, gluconate, lactate, glycinate,glutamate, ascorbate, aspartate, nitrate, phosphate, hydrogenphosphate,dihydrogenphosphate, formate, malonate, maleate, succinate, carbonate,bicarbonate, sulfate and hydrogensulfate. A salt of particular utilityis NaCl. As will be appreciated by those skilled in the art, while itmay be possible under certain circumstances to add a salt directly to aportion of the mixture during manufacturing, it is preferred to add thesalt as a mixture or solution of the salt in a carrier or solvent,particularly water. Of course, various concentration of the salt can bemade such as in the range of 1-40%, particularly 10-30% and, moreparticularly, 25-30%.

The stability of the emulsions of the invention may be measured by (1)visually evaluating the emulsions for phase separation and (2) for gels,further monitoring the rheology using the viscosity tests describedbelow.

The compositions of the present invention can include other optionalingredients to improve the aesthetics and/or performance of the cosmeticcompositions of the invention. These include colorants, fillers,fragrances, emollients, masking agents, water soluble emollients,hydrogen bonding modifiers (for example, urea, guanidine hydrochloride,xylitol, trehalose, maltose and glycerine), additional fragrances,additional preservatives, etc. Such one or more other optionalingredients can be added to the internal or external phases or both inappropriate amounts. For example, fragrances will frequently bepartitioned to both the external and internal phases regardless of whenor to what phase (or final product) the fragrance is added.

In a preferred embodiment the refractive indices of the external andinternal phases are matched within 0.005 to obtain a clear product.

The release of antiperspirant actives into the sweat is a significantevent in the development of an antiperspirant effect. The magnitude ofthe antiperspirant effect is related to the concentration of theantiperspirant salt in the sweat, and therefore measuring theconcentration of antiperspirant salt can provide an estimate ofantiperspirant efficacy. A variety of methods can be used to evaluateantiperspirant salt concentration, ranging from atomic absorption, ICP,and HPLC to solution conductance of aqueous films. The later method isespecially well suited for measuring the release of small amounts ofantiperspirant salts. The methods outlined below use solutionconductance to estimate antiperspirant salt release upon short exposuresto deionized water.

As noted above, the conductance of the compositions of the invention isdefined with reference to a value of at least 250 micro Siemens/crn/mlwhen the composition is loaded with at least 7% of an antiperspirantactive (such as the antiperspirant actives listed above) and when theconductance is measured by a fixed geometry test. For purposes ofclarification it should be explained that there are a variety of testsand test conditions that can be used to evaluate:

(1) “Conductance” is defined as an absolute measure of current flowthrough a solution with the dimensions of micro Siemens/cm, which valueis independent of probe geometry. This value is divided by the volume(in ml) of applied water to give the conductance number with the unitsof micro Siemens/cm/ml. This test is deemed a more reproduciblemeasurement since it references a set of fixed dimensions and units.

(2) Alternatively, “conductivity” as a measure of current flow through asolution without reference to probe geometry, and which is measured inmicro Siemens. This test is convenient for quick screening of solutions.

Standard Test for Thin Film Conductivity

One test for conductivity is called herein the “standard” test. Anon-conducting plastic block (for example, made from PLEXIGLASS®material) to form an oval shaped well 12.2 cm×2.5 cm with a depth of 100microns. This depth corresponds to the mean thickness of anantiperspirant product applied to the underarm of a human person duringreal use conditions (approximately 50 to 100 microns). An aliquot oftest sample is placed in the well of the block sufficient to fill thewell to the brim. Excess sample is scraped off by running a flat edgedinstrument over the surface of the block. The sample block, with theproduct film, is then either (a) equilibrated at room temperature fortwo hours or (b) placed in a synthetic underarm to simulate in vivoconditions. If method (b) is used, the air temperature inside thesynthetic underarm is maintained at 33 to 35° C. and a relative humidityof 85 to 95%, and the sample blocks are placed on a temperaturecontrolled surface maintained at body temperature (37° C.). Theseconditions closely approximate the temperature gradients normally foundin the underarm. Samples are equilibrated in either the (a) or (b)environments for two hours prior to measurement of antiperspirant saltrelease by solution conductivity. After two hours the sample blocks areremoved from the controlled environment and placed on a stage forconductivity measurement. An aliquot of 250 microliters of water with aresistance of at least 17 mega ohms is placed on the surface of thesample film, and the conductance of the water is measured as a functionof time with a Skicon 200 Skin surface Hygrometer (I.B.S. Co., Ltd.,Shizuoka-ken, 430, Japan) using an Elsnau (MT-8C Probe) electrode (ToddMaibach & Associates, San Francisco, Calif.). The electrode ispositioned so that it touches the bottom of the test sample in the well.Conductivity is measured in micro Siemens at 3.5 MHz. Data is collectedat 0.1 sec intervals for approximately 100 sec. Solution conductivityafter 10 seconds of exposure to the water is used to compare the releaseof active salt for different formulations This method is believed to beparticularly useful for evaluating the release of antiperspirant saltsin the absence of other salts. The standard method is useful as a quickscreening tool for active salt release studies. A solution conductivityof approximately 400 or greater micro Siemens at 10 sec afterapplication of the water droplet to the surface of the test sample, canbe considered evidence of significant release of the antiperspirantactive salt from the film surface and correlates with improvedantiperspirant efficacy.

Fixed Geometry Test for Thin Film Conductance

One of the limitations of the Standard Test is that the area of thewater droplet is not controlled and, therefore, the apparent conductance(which is measured as conductivity because the water volume is notcontrolled) is dependent on droplet spreading. This will lead to anunderestimate of the actual solution conductance (and thereforeantiperspirant salt release), of water drops which spread significantly.In order to measure the absolute concentration of the antiperspirantsalts the spreading of the water drop must be stopped. This can beaccomplished by placing a well of know dimensions on the surface of theproduct film to establish an area of constant size that is exposed tothe water droplet. A more predictable test is needed, such as the FixedGeometry Test.

The Fixed Geometry Test uses the same basic technique as the StandardTest in terms of preparation of the test well, addition of the testsample and equilibration of the sample to a selected temperature.Instead of allowing the water to flow freely on the surface of the testfilm, however, a second structure of non-conducing plastic predrilledwith holes of a fixed diameter is clamped over the well block. Thesecond structure with holes is also made of a non-conducting material(such as PLEXIGLAS material), is open on both ends and has an internaldiameter of 1.905 cm. The bottom of each predrilled hole is fitted witha small O-ring to prevent leakage of the water. A 400 microliter aliquotof water (rather than the 250 microliter aliquot used in the StandardTest) with a resistance of 17 mega Ohms is then placed in the hole tocover the test sample. This will normally result in a liquid height forwater of about 1.4 mm. The Elsnau probe is positioned through thedrilled hole so that the bottom of the probe rests on the bottom of thewell at a right angle. Because of the fixed shape, data can be obtainedas conductance in micro Siemens/cm/ml using the method described forcalculation.

As will be appreciated by those skilled in the art, a variety of othershapes, sizes and orientations of electrodes can be used. In anothervariation on the Fixed Geometry Test, thin gold wires (99% purity, setof 2, each about 1 mm in diameter) can be constructed to be in parallelwith the surface of the water (and covered by the water) and conductancecan be measured.

The electrode used in both types of tests must be calibrated so that aconductivity in micro Siemens can be obtained. Such calibration with asalt solutions in water of known conductance is known to those skilledin the art.

While different readings can be obtained depending on the thickness ofthe films, the test used, etc. it is important to establish a standardtest for purposes of defining conductivity according to this invention.The Fixed Geometry Test is set as the defining test because it isbelieved to be more reproducible. Thus a minimum conductance value of250 micro Siemens/cm/ml is the lower limit. Interestingly, minimumvalues for the Standard Test seemed to run about 400 micro Siemens dueto the way the test was conducted. For the data described here, samplesshould be placed in a chamber at the humidity and elevated temperatureconditions described above for about 2 hours. Samples not subjected toelevated temperatures should give higher values.

An average efficacy gel having a water content of greater than 35% (suchas Gillette's Right Guard Antiperspirant Gel) was compared with animproved gel made according to Example 12 below. The average efficacygel has a standard conductivity of 295±35 micro Siemens at 10 secondsand a fixed geometry conductivity of 121±47 micro Siemens/cm/ml at 10seconds. The improved formulation made according to this invention had astandard conductivity of 3554 micro Siemens at 10 seconds. The improvedformulation was ranked as above average in efficacy in a forearm testwhereas the average gel was ranked as average in efficacy in a clinicaltest.

While it is not known precisely how the compositions of this inventionwork, it has been observed that they have a combination of two importantproperties. These compositions exhibit superior stability on the shelfand yet degrade on contact with the skin to release the activeingredient with a higher level of efficacy than is usually achieved. Thedeodorant and/or antiperspirant compositions disclosed in this inventionform metastable emulsions when deposited on the skin. The decompositionof these emulsions upon application can be assessed by the thin filmconductance method described herein.

Particular formulations of interest include:

Formulation A

0.5-2.5% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))

55-65% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

1-10% PPG-3 myristyl ether

10-25% antiperspirant active (for example, Westchlor Zr 35 BX3 or SummitAZG-368)

10-25% water

0.5-1.5% fragrance

Formulation B

1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))

40-60% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

1-5% cyclomethicone (in addition to that found in the elastomer)

4-12% PPG-3 myristyl ether

15-30% antiperspirant active (for example, Westchlor Zr 35 BX3 or SummitAZG-368)

15-35% water

0.5-1.5% fragrance

Formulation C

1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))

1-10% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)

40-55% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

3-8% PPG-3 myristyl ether

15-20% antiperspirant active (for example, Westchlor Zr 35 BX3 or SummitAZG-368)

20-30% water

1.0-3.0% fragrance

Formulation D

1.0-3.0% dimethicone copolyol (for example, Corning 2-5185C (48%))

40-60% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

3-8% PPG-3 myristyl ether

15-30% antiperspirant active (for example, Westchlor Zr 35 BX3 or SummitAZG-368)

15-30% water

0.5-1.5% fragrance

1-10% diethylhexyl naphthalate

Formulation E

0.5-2.5% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))

60-70% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

7-10% antiperspirant active (for example, Westchlor Zr 35 BX3 or SummitAZG-368)

25-35% water

1-10% methylpropylene diol (MPDiol)

0.5-1.5% fragrance

Formulation F

1.0-3.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))

6-10% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)

35-45% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

6-10% PPG-3 myristyl ether

40-50% antiperspirant active as 43% active in water (for example, activeis Westchlor Zr 35 BX3 or Summit AZG-368)

no additional water

0.5-1.0% fragrance

Formulation G

0.1-0.6% dimethicone copolyol (for example, Corning 2-5185C (48%))

4-7% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)

40-50% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

4-7% PPG-3 myristyl ether

40-50% antiperspirant active as 43% active in water (for example, activeis Westchlor Zr 35 BX3 or Summit AZG-368)

no additional water

0.5-1.0% fragrance

Formulation H

0.5-2.0% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))

1-7% hydrogenated polyisobutene (for example, Fancol™ Polyiso 250)

40-50% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

45-55% antiperspirant active as 43% active in water (for example, activeis Westchlor Zr 35 BX3 or Summit AZG-368)

no additional water

0.5-1.5% fragrance

Formulation I

2-7% dimethicone copolyol (for example, Dow Corning 2-5185C (48%))

0.1-1% Oleath-20

1-5% C12-15 alkyl benzoate (Finsolv TN)

15-40% elastomer in cyclomethicone (for example, DC 9040 from DowCorning)

15-25% antiperspirant active (for example, active is Westchlor Zr 35 BX3or Summit AZG-368)

15-30% water

0.5-1.5% fragrance

The cosmetic composition according to the present invention can bepackaged in conventional containers, using conventional techniques.Where a gel, cream or soft-solid cosmetic composition is produced, thecomposition can be introduced into a dispensing package (for example,conventional packages for gels with glide on applicators, jars where thegel or cream is applied by hand, and newer style packages having a topsurface with pores) as conventionally done in the art. Thereafter, theproduct can be dispensed from the dispensing package as conventionallydone in the art, to deposit the active material, for example, on theskin. For roll-ons the compositions can be placed in a conventional typeof container. This provides good deposition of the active material onthe skin.

Compositions of the present invention can be formulated as clear,translucent or opaque products, although clear products are preferred. Adesired feature of the present invention is that a clear, ortransparent, cosmetic composition, (for example, a clear or transparentdeodorant or antiperspirant composition) can be provided. The term clearor transparent according to the present invention is intended to connoteits usual dictionary definition; thus, a clear liquid or gelantiperspirant composition of the present invention allows ready viewingof objects behind it. By contrast, a translucent composition, althoughallowing light to pass through, causes the light to be scattered so thatit will be impossible to see clearly objects behind the translucentcomposition. An opaque composition does not allow light to passtherethrough. Within the context of the present invention, a gel orstick is deemed to be transparent or clear if the maximum transmittanceof light of any wavelength in the range 400-800 nm through a sample 1 cmthick is at least 35%, preferably at least 50%. The gel or liquid isdeemed translucent if the maximum transmittance of such light throughthe sample is between 2% and less than 35%. A gel or liquid is deemedopaque if the maximum transmittance of light is less than 2%. Thetransmittance can be measured by placing a sample of the aforementionedthickness into a light beam of a spectrophotometer whose working rangeincludes the visible spectrum, such as a Bausch & Lomb Spectronic 88Spectrophotometer. As to this definition of clear, see European PatentApplication Publication No. 291,334 A2. Thus, according to the presentinvention, there are differences between transparent (clear),translucent and opaque compositions.

Compositions of the present invention may be made by the techniquesdescribed in the Examples below. In general, the external and internalphases are formed separately using heating with the addition of anon-ionic emulsifier as needed. The alcohol component is added to theinternal phase. The internal phase is added to the external phase veryslowly. After the addition has been completed, the mixture is stirred atspeeds on the order of 250-1000 rpm (for example, 700 rpm), to achieve ahomogeneous mixture, followed by homogenization at speeds which arecorrelated with a voltage setting of about 55-65, particularly 60, on aPowerstat Variable Autotransformer to achieve the target viscosity.Compositions with a viscosity of 0-50,000 centipoise, especially5,000-20,000 centipoise, may be suitable for roll-on products whilecompositions having a viscosity on the order of 50-400,000 centipoisemay be more suitable for soft solids or creams.

A variety of equipment and techniques may be used to obtain thecompositions of the invention, including one pass homogenization,colloidal mill. Examples of such equipment include Sonic ProductionSonolator 200-30, and Sonic Tri-Homo Colloid Mill both of which may beobtained from Sonic Corporation, Stratford, Conn.

It is believed that the more homogeneous the composition is and the moreuniform the particle size, the better properties of the composition.

Throughout the present specification, where compositions are describedas including or comprising specific components or materials, or wheremethods are described as including or comprising specific steps, it iscontemplated by the inventors that the compositions of the presentinvention also consist essentially of, or consist of, the recitedcomponents or materials, and also consist essentially of, or consist of,the recited steps. Accordingly, throughout the present disclosure anydescribed composition of the present invention can consist essentiallyof, or consist of, the recited components or materials, and anydescribed method of the present invention can consist essentially of, orconsist of, the recited steps.

EXAMPLES

The following Examples are offered as illustrative of the invention andare not to be construed as limitations thereon. In the Examples andelsewhere in the description of the invention, chemical symbols andterminology have their usual and customary meanings. In the Examples aselsewhere in this application values for n, m, etc. in formulas,molecular weights and degree of ethoxylation or propoxylation areaverages. Temperatures are in degrees C. unless otherwise indicated. Ifalcohol is used, it is 95% unless otherwise indicated. Unless otherwiseindicated, “water” or “D.I. water” mean deionized water. As is truethroughout the application, the amounts of the components are in weightpercents based on the standard described; if no other standard isdescribed then the total weight of the composition is to be inferred.Various names of chemical components include those listed in the CTFAInternational Cosmetic Ingredient Dictionary (Cosmetics, Toiletry andFragrance Association, Inc., 7^(th) ed. 1997). Viscosities are measuredusing Brookfield viscometers unless otherwise indicated. While specificamounts of particular elastomers have been described, there are chemicaldifferences in the variety of elastomers that are available. The use ofdifferent elastomers may result in the need to increase or decrease theamount of elastomer used in a particular formulation, especially if aclear product is desired.

Example 1 General Method

In general, the external and internal phases are formed separatelyeither at room temperature or with heating as described below. Theinternal phase is added to the external phase very slowly while stirringat to form an emulsion. After the addition has been completed, themixture is stirred at higher speed to achieve a homogeneous mixture. Thefinal formula viscosity is then achieved by homogenizing the emulsionunder either batch or continuous process conditions as described below.The fragrance may be added at any time during the process prior to finalhomogenization.

Preparation of the External Phase

The ingredients to be used in the external phase (including theelastomer) are weighed out at room temperature and combined in asuitable vessel such as a 2 liter glass beaker. The mixture is stirredat about 500 rpm for 15-20 minutes using an overhead mixer such as aLightnin Mixer Model L1003. If a waxy or solid emollient is to be addedto the external (also called “continuous”) phase, the mixture may beheated to facilitate dissolution while stirring then cooled to roomtemperature prior to combination with the internal phase as describedbelow. The elastomer component is obtained as a suspension of elastomerin cyclomethicone (for example at a concentration of 6% active in D5cyclomethicone). The elastomer component is added to the external phasewith stirring at high speed (500-700 rpm for a 0.5 kilogram batch) untilno particles of elastomer are visible to the eye.

Preparation of the Internal Phase

The internal dispersed phase is prepared as described below. Ingredientsare mixed for a time sufficient to achieve homogeneity. Theantiperspirant active used (for example, Westchlor Zr 35 BX3 (forexample, 43% aluminum-zirconium glycinate in water) is weighed into alarge beaker equipped with an overhead stirrer. Other internal phaseingredients are then added while stirring.

The fragrance (if any is used) is added last and may be added to theexternal phase normally (although it may be added to either the externalphase or the internal phase if alcohol is used in the formulation) orthe final formula prior to homogenization. For many of the examplesdescribed here, one could add the fragrance to the external phase.

If an optional non-ionic emulsifier such as Oleath-20 is used, theemulsifier and propylene glycol are combined in a separate beaker andheated to 40 degrees C. with stirring until the non-ionic emulsifiercompletely dissolved. The heat is turned off and the remainingingredients to be used in the internal phase, including theantiperspirant active are weighed out and added to the mixture ofpropylene glycol and non-ionic emulsifier.

If water or a salt solution are used, the internal phase is prepared asfollows. The solution containing antiperspirant active salt as receivedfrom supplier is weighed into a large beaker equipped with a magneticstirrer. Additional ingredients such as propylene glycol, ethanol andwater are added while stirring. If a salt water solution is used (suchas for NaCl, etc.), the salt water solution is prepared by dissolvingthe crystalline salt in water in a separate beaker and stirring untildissolved. The salt water solution is then added to the rest of theinternal phase and the mixture is stirred until homogeneous.

Preparation of the Emulsion

The internal phase made as described above is then added to the externalphase over the course of 15-30 minutes while stirring at a speed of500-700 rpm. After the addition is complete, the mixture is stirred at500-700 rpm for 20 minutes using a Lightnin Mixer Model L1003. Themixture is then homogenized for 2-4 minutes (especially 3 minutes) usinga homogenizer from Greerco Corp., Hudson, N.H. at a reading of about 60on a Powerstat Variable Autotransformer from Superior Electric Co.,Bristol, Conn.

Further Processing

The product is then further processed by homogenization to achieve thedesired final viscosity. This can be done by using a Gilford-Wood Model1-L (Greerco Corp., Hudson, N.H.) homogenizer. The homogenizer speed iscontrolled by a Powerstat Variable Autotransformer Type 3PN116B(Superior Electronic. Co., Bristol, Conn.). Typical voltage setting andprocessing time are chosen to give a desired final formula viscosity.

An other method of homogenization of the final product is to pass theemulsion through a colloid mill such as a Sonic Tri-Homo Colloid Mill ora process sonolator such Sonic Production Sonolator 200-30 bothavailable from Sonic Corporation of Stratford, Conn. Process conditionsare chosen to give the desired final product viscosity.

Example 2 Evaluation of Viscosity

Brookfield Viscosity

Viscosity can be measured using a Brookfield instrument (Model DV11+)with an E Spindle at 2.5 revolutions per minute (rpm) and a setting of S95. Units are in centipoise (“cps”).

Carri-Med Viscosity p A second way of evaluating rheology is with theuse of Carri-Med equipment to obtain complex viscosity. Rheologicalparameters can be measured using a Carri-Med CSL 100 instrument withparallel plates. Initially the zero gap is set on the instrument. Asample of approximately 5 grams is placed on the stage of theinstrument. A 15 minute compression is used for sample equilibration.The excess of the sample is scraped around the plate geometry. Therheological parameters G, G″, tan (delta) and complex viscosity (n*) canbe measured by torque sweep experiments. An acrylic plate 6 cm indiameter can be used. A gap (1000 microns) is used between the twoplates (acrylic plates 6 cm in diameter). Temperature is maintained at23 degrees C. The oscillation stress can be varied from 2.358 Pa to50.74 Pa with an oscillation frequency kept constant at 1 Hertz. Unitsare in Pascal seconds (“Pa sec”).

TABLE A Ingredient Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex.11 Ex. 12 Ex. 13 External Phase Elastomer (DC9040) 12% active) 55 62 6240 41.5 25 31.5 21 17 17 50 Dimethicone copolyol (Dow Corning 1 2 2 4 11 2.5 1 1 1 2 2-5185, 48% active in cyclomethicone) Hydrogenatedpolyisobutene 5 — — 8 5 — 5 1.5 1.5 1.5 — (Polyiso 250) PPG-3 MyristylEther 3 4.5 5 — 5 5 — 0.5 0.5 0.5 5.0 C12-15 alkyl benzoate — — — 2 — —— — — — — (FINSOLV TN) Cyclomethicone (Dow Corning 245) — — — — — — — 59.0 9.0 2.0 Fragrance 1 1 1 1 1 1 1 1 1 1 1 Internal PhaseAntiperspirant Active^(a) 15 15.5 30 19.5 46.5 48.45 60.0 60.5 63.6860.13 20 Water (deionized)^(b) 20 15 25 19.55 9.5 6.32 9.87 20 Oleath-20(HLB > 8) — — — 0.5 — — — — — — — Total 100 100 100 100 100 100 100 100100 100 100 ^(a)= See explanation of actives used. ^(b)= Note that inthe examples, sometimes the antiperspirant active is listed as asolution (which will include a water component) under the “active”designation with little or no water and sometimes the active and waterare listed separately.

Examples 3-13 Compositions

The method described in Example 1 was used to make the compositionslisted in Table A with the types and amounts of ingredients listed inthe Table. Amounts are in percent by weight based on the total weight ofthe composition.

With regard to the active ingredients used, Westchlor Zr 35BX3 (77%solid actives on an anhydrous basis) dissolved in water was used forExamples 3, 4, 6 and 13. Westchlor Zr BX3 (33.55% actives on ananhydrous basis in water) was used for Example 7. An active as preparedby the method of Example 14 (41.28% solids on an anhydrous basisdissolved in water) was used for Examples 5 and 8. An active as preparedby the method of Example 14 (31.16% solids on an anhydrous basisdissolved in water) was used for Example 11. Summit AZG 368 (32% activeson an anhydrous basis dissolved in water) was used for Example 9. Anactive as prepared by Example 14 (33% actives on an anhydrous basisdissolved in water) was used for Examples 10 and 12.

TABLE B Property Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11Ex. 12 Ex. 13 Initial Brookfield Viscosity (centipoise) 240,000 170,000310,000 185,000 132,000 205,000 280,000 320,000 225,000 260,000 270,000Brookfield Viscosity after 4 weeks at 49° C. 140,000 210,000 278,000270,000 (centipoise) Initial Carri-Med Complex Viscosity    220    283   339    467    206 (Pascal seconds) Carri-Med Complex Viscosity(Pascal    213    274    319    515    140 seconds) after 4 weeks at 49°C.

Examples 3-13 Viscosity

The viscosity of Examples 3-13 was evaluated using the method of Example2 to obtain viscosity data from the Brookfield method and rheology datafrom the Carri-Med method. The data is shown in Table B.

Examples 3-13 Clarity

The clarity of Examples 3-13 was evaluated using visual observation.Compositions made according to Examples 3, 6, 7, 8, 9, 10, 11 and 12gave clear products. Compositions made according to Examples 4 and 5gave products that were not clear. A composition made according toExample 13 gave a translucent product.

Examples 3-13 Conductivity

The Standard Method described above was used with a 250 microliter dropof water placed on a 100 micron thick film of the test formula. Beforethe test each sample was equilibrated for 2 hours at 35 degrees C. and85% relative humidity (simulation of underarm conditions). Since theFixed Geometry Method was not used to obtain conductance data, for thelisted Examples, the diameter of the spreading of the water drop isgiven. As noted above a minimum of 250 micro Siemens for the FixedGeometry Method is the defined lower limit. Readings for conductivityusing the Standard Method will be somewhat higher. The Control GelExample was prepared using the same procedure as described for Examples3-13 with 5% dimethicone copolyol (Dow Corning 2-5185 diluted to 40%);1% Cyclomethicone (DC 245 (D5)); 53.37% antiperspirant active (28% inpropylene glycol) (Westchlor 4105); 6.08% propylene glycol; 9.12%alcohol (SDA 40 200); 1.0% fragrance; 0.23% Tween 80; and 8.5% elastomer(5.8% actives in D5 cyclomethicone—elastomer described in U.S. Pat. No.6,060,546). The Control Stick Example was Lady Speed Stick. The datashows that emulsion of the invention has conductivity as good as orbetter than the stick.

The samples were prepared by matching the RI's of the two phases (within0.005) and samples were visually observed to be clear.

Conductivity was evaluated for selected Examples using the StandardMethod. The results are listed in TABLE C.

TABLE C Property Ex. 3 Ex. 5 Ex. 7 Ex. 8 Ex. 9 Ex. 11 Ex. 12 Ex. 13Conductivity at 100 seconds (micro Siemens) 2182 851 701 4798 4216 55484403 3880 Diameter of water droplet after spreading (cm) 2.1 1.3 — 5.44.5 4.8 3.1 3.3 Conductivity at 10 seconds (micro Siemens) 1527 547 5094511 3987 4842 3554 3412 % oil phase 65 70 53.5 32 40.0 30 30 60

The data in Table C may be compared with the data in Table D which isdata for controls. Control stick #1 is Lady Speed Stick® antiperspirant(Mennen), and Control stick #2 is Right Guard® antiperspirant(Gillette). Normally a gel product does not have very good conductivitywhile stick products have much better conductivity. The data in Table Cshows that compositions of the present invention have conductivityvalues comparable to stick products.

TABLE D Control Control Stick Control Property Gel #1 #1 Gel #2Conductivity at 100 seconds (micro 180 3077 Siemens) Diameter of waterdroplet after 0.87 1.7 1.2 spreading (cm) Conductivity at 10 seconds(micro 154 1627 295 ± 35 Siemens) % oil phase 30 (suspension) 20

Examples 14-16 Experimental Antiperspirant Salts

Improved aluminum zirconium tetrachlorohydrex gly salt can be made usingthe following Examples 13-15. The goal is to enhance the smallest Alspecies (Peak-5) by lowering the metal:chloride molar ratio of thetetra-salt to be in the range of 1.2-0.9:1 and to stabilize the Zrpolymeric species by raising the glycine/Zr molar ratio to be greaterthan 1.4:1.

Example 14

Glycine powder (159 g) is added to a zirconium compound (1000 g of a 31%solution of zirconium oxychloride (ZrOCl₂)) with stirring. Aluminumchlorohydrate (“ACH”) (1120 g of a 50% aqueous ACH solution) is thenadded with additional stirring. The final solution is then diluted withdistilled water into an anhydrous concentration of 33.0%, with aglycine/zirconium molar ratio of 1.45:1; aluminum/zirconium molar ratioof 3.56:1, and metal/chloride ratio of 1.01:1.

Example 15

Glycine powder (159 g) is added to a zirconium compound (1000 g of a 31%solution of zirconium oxychloride (ZrOCl₂) with stirring. ACH (1204 g ofa 50% aqueous ACH solution) is then added with additional stirring. Thefinal solution is then diluted with distilled water into an anhydrousconcentration of 30.0% with a glycine/zirconium molar ratio as 1.45:1;an aluminum/zirconium molar ratio of 3.82:1, and a metal/chloride ratioof 0.98.

Example 16

A solution of AlCl₃ (200 g of 28% aqueous solution) is added to a ZAGsolution (800 g of a 43% solution of Westchlor Zr 35BX3) with stirring.The mixture is then diluted into an anhydrous concentration of 30%. Thefinal solution has an aluminum/zirconium molar ratio of 4.36:1; ametal/chloride ratio of 0.94:1; and a glycine/zirconium ratio of 0.97:1.

Analytical Data for Examples 14-16

Size exclusion chromatography (“SEC”) or gel permeation chromatography(“GPC”) are methods frequently used for obtaining information on polymerdistribution in antiperspirant salt solutions. With appropriatechromatographic columns, at least five distinctive groups of polymerspecies can be detected in a ZAG, appearing in a chromatogram as peaks1, 2, 3, 4 and a peak known as “5,6”. Peak 1 is the larger Zr species(greater than 120-125 Å). Peaks 2 and 3 are larger aluminum species.Peak 4 is smaller aluminum species (aluminum oligomers) and has beencorrelated with enhanced efficacy for both ACH and ZAG salts. Peak 5,6is the smallest aluminum species. The relative retention time (“Kd”) foreach of these peaks varies depending on the experimental conditions.Data for Table E was obtained by using the methods described in ourpatent U.S. Pat. No. 5,997,850, incorporated by reference herein as tothe description of analytical techniques for obtaining peak analyses.

TABLE E Polymer Distribution of the Improved Salts (SEC analysis)Peak-1/ Peak-4/ Peak-3 Peak-2/Peak-3 Peak-3 Peak-5/Peak-3 Example 14 00.2 0.24 3.11 Example 15 0 0.03 0.17 1.71 Example 16 0.95 0.34 0.27 2.60WZR35BX3^(a) 0.55 0.24 0.18 0.55 a = commercial salt from Westwood.

We claim:
 1. A clear antiperspirant and/or deodorant composition in theform of an emulsion having a refractive index less than 1.42 andcomprising: (a) 25-70% of an external phase comprising: (i) 0.1-10%, onan actives basis, of at least one elastomer which is a cyclomethicone(and) dimethicone crosspolymer made with an ≡Si—H containingpolysiloxane and an alpha, omega-diene of formula CH₂═CH(CH₂)_(x)CH═CH₂,where x=1-20, to form a gel by crosslinking and addition of ≡Si—H acrossdouble bonds in the alpha, omega diene, which crosspolymer has aviscosity in the range of 50,000-3,000,000 centipoise; (ii) 0.1-5% of asilicone copolyol having an HLB value ≦8; (iii) 0.1-68% of a volatilesilicone selected in an amount to complete the external phase; (iv)0-10% of a cosurfactant or emulsifier having an HLB value in the rangeof 1-15; (v) 0-5% of a non-volatile silicone; and (b) 30-75% of aninternal phase which is made with: (i) 7-25% (on an anhydrous activesbasis (excluding the waters of hydration) of an antiperspirant active;(ii) 0-10% ethanol; (iii) additional water as required to adjust therefractive index; (iv) 0-5% of an antimicrobial agent; and (v) 0-5% ofan ionizable salt; wherein (1) the conductance of a water dropletapplied to the surface of a thin film of the antiperspirant and/ordeodorant composition is at least 250 micro Siemens/cm/ml as measured bya fixed geometry test at a loading of at least 7% by weight level ofantiperspirant active; and (2) all amounts are in percent by weightbased on the total weight of the composition.
 2. A clear antiperspirantand/or deodorant composition according to claim 1 having an oil contentof 25-50%.
 3. A clear antiperspirant and/or deodorant compositionaccording to claim 1 having an oil content of 30-45%.
 4. A clearantiperspirant and/or deodorant composition according to claim 1 havingan oil content of 40-70%.
 5. A clear antiperspirant and/or deodorantcomposition according to claim 1 having an oil content of 30-60%.
 6. Aclear antiperspirant and/or deodorant composition according to claim 1comprising 1-5% of the elastomer in cyclomethicone.
 7. A clearantiperspirant and/or deodorant composition according to claim 1comprising 0.1-1.0% of the silicone copolyol.
 8. A clear antiperspirantand/or deodorant composition according to claim 1 wherein the siliconecopolyol is one or more dimethicone copolyols.
 9. A clear antiperspirantand/or deodorant composition according to claim 1 comprising 0-5% of thecosurfactant or emulsifier.
 10. A clear antiperspirant and/or deodorantcomposition according to claim 1 wherein the cosurfactant or emulsifieris one or more members selected from the group consisting of: (a)sorbitan esters and ethoxylated sorbitan esters selected from the groupconsisting of PEG-20 sorbitan isostearate, sorbitan monolaurate,polysorbate-20, polysorbate-40, polysorbate-60, and polysorbate-80; (b)ethoxylates selected from the group consisting of Ceteth-20, PEG-30castor oil, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castoroil, Laureth-7, Isolaureth-6, Steareth-10, Steareth-20, Steareth-21,Steareth-100, Ceteareth-12, Oleth-5, Oleth-10, and Oleath-20; (c)ethoxylated adducts selected from the group consisting of PEG-25stearate, glyceryl stearate and PEG-100 stearate; (d) PEG estersselected from the group consisting of PEG-8 oleate, PEG-8 laurate, PEG-8dilaurate, PEG-12 dilaurate, PEG-80 diisostearate, and PEG-40 stearate;(e) propoxylates selected from the group consisting of PPG-10butanediol, PPG-50 oleyl ether, PPG-2-ceteareth-9, PPG-3-deceth-3, andPPG-5-ceteth-20; (f) ethoxylated modified triglycerides selected fromthe group consisting of PEG-20 corn glycerides, and PEG-12 palm kernelglycerides; (g) alkylphenol aromatic ethoxylates selected from the groupconsisting of dinonylphenol ethoxylate with 9 moles of ethylene oxide,octylphenol ethoxylate with 20 moles of ethylene oxide, octylphenolethoxylate with 40 moles of ethylene oxide; and (h) block copolymerswhich are alkoxylated glycols having ethoxylated and propoxylatedsegments and which are selected from the group consisting of Poloxamer182, Poloxamer 234, and Meroxapol
 174. 11. A clear antiperspirant and/ordeodorant composition according to claim 1 wherein the volatile siliconeis added in an amount of 20-58%.
 12. A clear antiperspirant and/ordeodorant composition according to claim 1 wherein the volatile siliconeis added in an amount of 20-50%.
 13. A clear antiperspirant and/ordeodorant composition according to claim 1 wherein the volatile siliconehas a boiling point≦250 degrees C. at one atmosphere of pressure and isone or more members of the group consisting of (a) cyclicpolydimethylsiloxanes represented by Formula III:

where n is an integer with a value of 3-7; and (b) linearpolydimethylsiloxanes represented by Formula IV:

and t is selected to obtain a viscosity of 1-200 centistokes.
 14. Aclear antiperspirant and/or deodorant composition according to claim 1wherein the non-volatile silicone has a boiling point greater than 250degrees at one atmosphere of pressure.
 15. A clear antiperspirant and/ordeodorant composition according to claim 1 wherein the non-volatilesilicone is one or more members selected from the group consisting ofphenyl trimethicone, dimethicone, phenylpropyltrimethicone, cetyldimethicone, and dimethiconol.
 16. A clear antiperspirant and/ordeodorant composition according to claim 1 wherein the antiperspirantactive is one or more members selected from the group consisting ofaluminum salts, aluminum/zirconium salts, aluminum/zirconium saltscomplexed with a neutral amino acid.
 17. A clear antiperspirant and/ordeodorant composition according to claim 1 wherein the antiperspirantactive is one or more members selected from the group consisting ofaluminum chlorides, zirconyl hydroxychlorides, zirconyl oxychlorides,basic aluminum chlorides, basic aluminum chlorides combined withzirconyl oxychlorides and hydroxychlorides, and organic complexes ofeach of basic aluminum chlorides with or without zirconyl oxychloridesand hydroxychlorides and mixtures of any of the foregoing.
 18. A clearantiperspirant and/or deodorant composition according to claim 1 whereinthe antiperspirant active is one or more members selected from the groupconsisting of aluminum chlorohydrate, aluminum chloride, aluminumsesquichlorohydrate, aluminum chlorohydrol-propylene glycol complex,zirconyl hydroxychloride, aluminum-zirconium glycine complex, aluminumdichlorohydrate, aluminum chlorohydrex PG, aluminum chlorohydrex PEG,aluminum dichlorohydrex PG, aluminum dichlorohydrex PEG, aluminumzirconium trichlorohydrex gly propylene glycol complex, aluminumzirconium trichlorohydrex gly dipropylene glycol complex, aluminumzirconium tetrachlorohydrex gly propylene glycol complex, and aluminumzirconium tetrachlorohydrex gly dipropylene glycol complex.
 19. A clearantiperspirant and/or deodorant composition according to claim 1 whereinthe antiperspirant active is added to the composition in the form of asolution.
 20. A clear antiperspirant and/or deodorant compositionaccording to claim 1 wherein the antiperspirant active has ametal:chloride molar ratio in the range of 0.9-1.2:1 and aglycine:zirconium ratio greater than 1.4:1.
 21. A clear antiperspirantand/or deodorant composition according to claim 20 wherein theantiperspirant active has a metal:chloride molar ratio in the range of0.9-1.1:1.
 22. A clear antiperspirant and/or deodorant compositionaccording to claim 1 comprising an antimicrobial agent.
 23. A clearantiperspirant and/or deodorant composition according to claim 1comprising an ionizable salt of the form M_(a)X_(b) where a=1 or 2; b=1or 2; M is a member selected from the group consisting of Na⁺¹, Li⁺¹,K⁺¹, Mg⁺², Ca⁺², Sr⁺², Sn⁺², and Zn⁺², and X is a member selected fromthe group consisting of chloride, bromide, iodide, citrate, gluconate,lactate, glycinate, glutamate, ascorbate, aspartate, nitrate, phosphate,hydrogenphosphate, dihydrogenphosphate, formate, malonate, maleate,succinate, carbonate, bicarbonate, sulfate and hydrogensulfate.
 24. Aclear antiperspirant and/or deodorant composition according to claim 1additionally comprising 0.5-50% of an emollient.
 25. A clearantiperspirant and/or deodorant composition according to claim 24wherein the emollient is selected from the group consisting of (a) fatsand oils which are natural or synthetic glyceryl esters of fatty acidshaving a general structure of Formula VI:

wherein each of R¹, R², and R³ may be the same or different and have acarbon chain length (saturated or unsaturated) of 7 to 30; (b)hydrocarbons selected from the group consisting of paraffins,petrolatum, hydrogenated polyisobutene, and mineral oil, (c) esters offormula R⁴CO—OR⁵ wherein the chain length for R⁴ and R⁵ is independentlyselected to be in the range of from 7 to 30, R⁴ and R⁵ and can besaturated or unsaturated, straight chained or branched; (d) saturatedand unsaturated fatty acids having a formula R⁶COOH wherein R⁶ has acarbon chain length from 7 to 30 and is straight chain or branched; (e)saturated and unsaturated fatty alcohols having a formula R⁷COH where R⁷has a carbon chain length from 7 to 30 and is straight chain orbranched; (f) lanolin and its derivatives having a formulaR⁸CH₂—(OCH₂CH₂)_(n)OH wherein R⁸ represents the fatty groups derivedfrom lanolin and n=5 to 75 or R⁹CO—(OCH₂—CH₂)_(n)OH where R⁹CO—represents the fatty acids derived from lanolin and n=5 to 100; (g)alkoxylated alcohols wherein the alcohol portion is selected fromaliphatic alcohols having 2-18 carbons, and the alkylene portion isselected from the group consisting of ethylene oxide, and propyleneoxide having a number of alkylene oxide units from 2-53; (h) ethersselected from the group consisting of dicaprylyl ether; dicetyl ether;dimethyl ether; distearyl ether; ethyl ether; isopropyl hydroxycetylether; methyl hexyl ether; polyvinyl methyl ether; (i) silicones andsilanes which are members of the group consisting of: (1)(R¹⁰)₃SiO(Si(R¹¹)₂O)_(x)Si(R¹²)₃ where R¹⁰, R¹¹ and R¹² can be the sameor different and are each independently selected from the groupconsisting of phenyl and C1-C60 alkyl; (2)HO(R¹⁴)₂SiO(Si(R¹⁵)₂O)_(x)Si(R¹⁶)₂OH, where R¹⁴, R¹⁵ and R¹⁶ and be thesame or different and are each independently selected from the groupconsisting of phenyl and C1-C60 alkyl; or (3) organo substituted siliconcompounds of formula R¹⁷Si(R¹⁸)OSiR¹⁹ which are not polymeric where R¹⁷,R¹⁸ and R¹⁹ can be the same or different and are each independentlyselected from the group consisting of phenyl and C1-C60 alkyl optionallywith one or both of the terminal R groups also containing an hydroxylgroup; (i) adipic acid blends selected from the group consisting oftrimethyl pentanediol/adipic acid copolymer; trimethylpentanediol/adipic acid/isononanoic acid copolymer; and adipicacid/diethylene glycol/glycerin crosspolymer; and (j) mixtures andblends of two or more of the foregoing.
 26. A clear antiperspirantand/or deodorant composition according to claim 1 wherein theconductance is greater than 300 micro Siemens/cm/ml.
 27. A clearantiperspirant and/or deodorant composition according to claim 1 whereinthe conductance is greater than 400 micro Siemens/cm/ml.
 28. A clearantiperspirant and/or deodorant composition according to claim 1 whereinthe conductance is greater than 500 micro Siemens/cm/ml.
 29. A clearantiperspirant and/or deodorant composition according to claim 1 whereinthe elastomer has a viscosity in the range of 100,000-1,000,000centipoise.
 30. A clear antiperspirant and/or deodorant compositionaccording to claim 1 wherein the elastomer has a viscosity in the rangeof 250,000-450,000 centipoise.